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Communication: Tunnelling splitting in the phosphine molecule
R. P. Bell, The Tunnel Effect in Chemistry (Springer, 1980), pp. 51–76.
O. N. Ulenikov, E. S. Bekhtereva, V. A. Kozinskaia, J. J. Zheng, S. G. He, S. M. Hu, Q. S. Zhu, C. Leroy, and L. Pluchart, J. Mol. Spectrosc. 215, 295 (2002).
B. Noumeroff, “Méthode nouvelle de la détermination des orbites et le calcul des éphémérides en tenant compte des perturbations,” in Trudy Glavnoi Rossiiskoi Astrofizicheskoj Observatorii (Gosudarsvennoe Izdatel’stvo, Moscow, 1923), Vol. 2, pp. 188–259.
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Splitting due to tunnelling via the potential energy barrier has played a significant role in the study of molecular spectra since the early days of spectroscopy. The observation of the ammonia doublet led to attempts to find a phosphine analogous, but these have so far failed due to its considerably higher barrier. Full dimensional, variational nuclear motion calculations are used to predict splittings as a function of excitation energy. Simulated spectra suggest that such splittings should be observable in the near infrared via overtones of the ν
2 bending mode starting with 4ν
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